Anthrapyridone dye developers



3,076,808 srramomt nrnnnvnrornas and to Elkan R. Blout, Belmont, Sidney Kasman, Arlington,

Myron 5. Simon, Mass, assrgnors Polaroid Corporation, Cambridge, Mass, a corporation of Delaware No-Drawing. Filed Nov-.7, 1961, Ser. No. 150,661

9 Claims- (Cl. 260-278) This invention relates to photography and more. particularly to products, compositions. and processes for. the

development. of photosensitive silver halide elements.

It is one object of the presentinvention to provide novel processes and compositions for the development of silver halide emulsions, in which novel colored silver halide developing agents are used.

Another object is to provide novel processes and compositions for the development of silver halide emulsions, in which the novel silver halide developing agent is capable of developing an exposed silver halide emulsion and imparting a reversed or. positive colored image of the developed image to a superposed image-receiving material.

Further objects are to provide said novel silver halide developing agents, and novel products, processes and compositions suitable for use in preparing monochromatic and multichromatic photographic images by the employment of said novel silver halide developing agents.

Other objects, of the invention will in part be obvious and will in part appearv hereinafter.

The invention accordingly comprises the processes involving the several steps and the relation and order of one or more of such steps with respect to each ofthe others, and the products and compositions possessing the features, properties and. the relation of elements which are exemplified in the following detailed disclosure, and the scope of the application of which will be indicated in the claims.

The objects of this invention may be accomplished by the use of certain novel, dyes which have the ability to develop an exposed silver halide emulsion; thus these These novel described hereindyes; may be referred to as dye developers. dyes or dye developerswill be further after.

The dye the-photographic processes and compositions disclosed herein are particularly useful in the treatment of an exposed s1lver halide emulsion,,whereby a positive dye image may be imparted toanother element, herein referred to asan image-carryingv or imagereceiving element.

US. Patent No. 2,983,606, issued May 9, 1961, to Howard G. Rogers, discloses diffusion transfer processes wherein. a. photographic negative material,v such as a photogra hic element comprising an exposed silver halide emulsion, is developed in the dye developer to impart to an image-receiving layer a reversed orpositive dye image. of the developed image by permeating into said emulsion a suitable liquid processing composition and bringing said emulsion with an appropriate imagereceiving layer. The inventive concepts herein set forthprovid'enovel. dye developers which may be advantageously used in such processes.

in carrying out the process of this invention, a photosensitive element containing a silver exposed and wetted with a liquid processing composition, for example, by immersing, coating, spraying, flowing, etc., in the dark, photosensitive element superposed prior to, during or ceiving element. sensitive element contains a the liquid processing composition is ap lied to the photosensitive element in a element is brought into superposed position with an imageinto superposed relationship halide emulsion is.

contrast in the positive image, and

vi'ding an imagewise to provide a United States Patt1tQffiC PM 2. receiving element. The liquid processing composition permeates the emulsion to provide a solution of dye developer substantially uniformly distributed therein. As the exposed silver halide emulsion is developed, the oxidation product of the dye developer is immobilized or precipitated in situ with the developed silver, thereby prodistribution of unoxidized dye d veloper dissolved in the liquid processing composition. This immobilization is apparently due, at least in part, to a change. in the solubility characteristics ofthe dye developer upon oxidation, and especially as regards its solubility in alkaline solutions. It may also be due, in part, to a tanning effect on the emulsion by the oxidized developing agen At least part of this imagewise distribution of unoxidized dye developer is transferred, by imbibition, to a superposed image-receiving layer. The image-receiving layer receives a depthwise diffusion, the emulsion, of unoxidized dye developer, without appreciably disturbing the imagewise distribution thereof, 7 reversed or positive, colored image of the developed or negative image. The image-receiving element may contain agents adapted to mordant or otherwise fix the diffused, unoxidized dye developed. Imbibition periods of. approximately one minute have been found to give good results, but this contact period may be adjusted where necessary to compensate for variations in temperature or other conditions. The desired positive image isrevealed by separating the image-receiving layer from the silver halide emulsion at the end of the imbibition period.

The dye developers of this invention may be utilized in the photosensitive element, for example in, on or behind the silver halide emulsion, or they may be utilized in the image-receiving element orin the liquid processing comosition. In a preferred embodiment, a coating or layer of the dye developer is placed behind the silver halide emulsion, i.e.,. on the side of the emulsion adapted to be located most distant from the photographed subject when the emulsion is exposed and preferably also adapted to be most distant from the image-receiving layer when in superposed relationship therewith. Placing the dye developer behind the emulsion layer, as in the preferred embodiment, has the advantage of providing increased also minimizes any light-filtering action by the colored dye developer. in this preferred embodiment, the layer of dye developer may be applied by using a coating solution containing, e.g., about 0.5 to 8%, byweight, of the dye developer. Similar concentrations may be used if the dye developer is utilized as a component ofv the liquid processing composition; In an especially useful mode of disposing the dye developers in the photosensitive elements, the dye developer is dissolved in a water-immiscible solvent and then dispersed inla gelatin coating solution.

The liquid processing composition which is used in the processes herein disclosed comprises at least an aqueous solution of an alkaline compound, for example, diethylamine, sodium hydroxide or sodium carbonate, and may contain the dye developer. in some instances, it may contain an additional silver halide developing agent. the liquid processing composition is to be applied to the emulsion by being. spread thereon, preferably in a relatively thin, uniform layer,,it may also include a viscosityincreasing compound constituting film-forming material of the type which, when spreadover a water-absorbent base, will form a relatively firm and relatively stable film. A preferred film-forming material is a high molecular weight polymer such as a polymeric, water'soluble ether inert to an alkali solution, as, for example, a hydroxyethyl cellulose or sodium carboxymethyl cellulose. Other films-forming: materials orthickening agents whose ability an anthrapyridone, that is, a 3-azabenzanthrone, nucleus to V1 ich is attached at least one and preferably not more than two organic groups capable of functioning as silver halide developing groups.

1 to novel dye developers of the present invention cornprise anthrapyridone dyes characterized in that they contain at least one group of the formula:

an exposed silver halide emulsion.

In addition to the substituents which provide the silver halide developing function, Z may be substituted by halogen, alkoxy, alkyl, etc., radicals. The term amino as used herein is amino and arylatnino groups.

general, the developing group comprises a benzenoid deradicals such as alkylene radicals, ene radicals such as ethylene, isopropylene, etc.; sulfonamide; sulfamyl; carboxarnido; carbarnyl; arylene radicals such as phenylene, etc; aralkylene radicals such as phenethyl, etc; acyl radicals such as etc.; divalent radicals which contain both hetero and carbon atoms as constituent components, as for example,

etc; and suitable combinations thereof.

The anthrapyridone dye developers may be represented by the formula:

wherein:

Each of R R R R R R", R and R may be 1-Z, hydrogen, aryl, alkyl and preferably lower alkyl,

halogen, amino, cyano, acyl, nitro, carboallzoxy, carboxy sulfo, alkoxy, hydroxyl, carboxamido, or aralkyl;

R may be Y-Z, hydrogen, alkyl and preferabl lower alkyl, aryl or aralkyl;

-Y-Z has the same significance as previously noted At least one developing group YZ is present; And wherein more than one developing group YZ is present, each such group Y Z may be the same or different.

intended to include and B-hydroxyethyl, etc.

of anthrapyridone dye developers the formula:

of lower alkylene, sulfonamido, sulfamyl, carboxamido, carbamyl, phenylene,

O H @lower alkylene, lower alkylene-C- developing least one of As examples of useful anthrapyridone dye developers within the scope of the last-mentioned formula, mention may be made of the following compounds:

O L/K CHPC I T-om-onh anthrapyridone.

It has been found that anthrapyridone dye developers within'the preferred group, which have a 6-alkylamino or 6-arylarnino substituent, are magenta dye developers 40 having exceptionally good spectral,characteristics, since they absorponly a minimal amount of light which ideally should be transmitted. Thus, these dye developers are particularly useful in multicolor products and processes such are described in the aforementioned US. Patent No. 2,983,686. Moreover, those analogues having a 6-ary1- amino substituent have been found to possess unusually good stability. It will be appreciated that the alkylarnino 3 or arylamino substituent may in turn be substituted, as l illustrated in the above-named compounds, and may, for N example, contain a developing function.

- As examples of other anthrapyridone dye developers,

mention may be made of the following compounds. (8) 6H 3- 2' EZ-Gihydroxy henyD-a-methyl]-ethyl-6-[4'-B-(2" 5 55.1

[5 diliydroxyphenl)=ethy1]-anilino-anthrapyridone 0'. 14542';5'-dihydroxyphenyI)=u methy1]-ethy1%3rmethylanthrapyridone,

OH O I H n I H o ILTH-QCHz-CH The anthrapyridone dye developers of this invention may be prepared by methods similar to those used to prepare anthrapyridone dyes. Thus, the anthrapyridone dye developers may be synthesized by cyclization of 1-acetarnidoanthraquinones, the acetyl group of which may be unsubstituted or substituted, for example, preferably substituted with a halogen group such as chlorine, by ester condensations with anthraquinones having a primary or secondary amino group alpha to a carbonyl group, e.g., l-arninoanthraquinone, or by cyclization of suitably substituted benzoic acids, e.g., m-carboxyanilides or phenylpropiolic acid, phenylpropionic acid or phenylpropargylio acid. The desired developer group or groups X may be introduced before or after formation of the anthrapyridone nucleus, as illustrated in Examples 1 and 2, respectively. It will be apparent that various groups may be substituted before or after formation of the anthrapyridone nucleus for the purpose of modifying the color, solubility, or other properties.

One preferred method of preparing the aforementioned anthrapyridone dye developers wherein the desired developer group or groups is introduced prior to formation of the anthrapyridone nucleus comprises condensing an anthraquinone dye having at least one group of the formula:

H -l\ r-Y-z wherein Y and Z have the same significance as previously set forth; substituted on the anthraquinone nucleus in u-position to a carbonyl group with an ester selected from the group consisting of acetoacetic, malonic and cyanoacetio esters.

The aforementioned ester condensations are preferably effected in the presence of a suitable catalyst, as for ex ample, a mixture of sodium acetate and cuprous chloride.

Another preferred method of preparing anthrapyridone dye developers wherein the desired developer group or groups is introduced prior to formation of the anthrapyridone nucleus comprises acetylating an anthraquinone dye developer having a secondary amino group, such as the aforementioned substituent wherein Z is an ortho or dihydroxyphenyl radical, substituted on the anthraquinone nucleus in a position a, to a carbonyl group and then internally condensing the acetylated compound to effect cyclization thereof to form the anthrapyridone. The acetylation may be accomplished, for example, by refluxing the anthraquinone dye developer with acetyl chloride. It should be noted that this treatment concurrently acetylates the developing group. The cyclization may be carried out, for example, by refluxing with an alkaline solution in an inert atmosphere, such as under a blanket of nitrogen. The acetylated developer group is hydrolyzed to the free developer during this cyclization.

A preferred method of preparing the aforementioned anthrapyridone dye developers wherein the desired develg oper group or groups is introduced subsequent to formation of the anthrapyridone nucleus comprises reacting an anthrapyridone dye having a nitro or halogen group substitutcd in position 6 with a compound of the formula:

wherein Y has the same significance as previously noted, X represents a primary or secondary amino group, and Z represents a protected developer group, e.g., 2',5-diacyloxyphenyl, etc.

Another method of preparing the aforementioned anthrapyridone dye developers comprises effecting a condensation reaction between an anthrapyridone dye having substituted thereon one or more sulfonyl chloride and/ or acid chloride groups and a compound within the lastmentioned formula.

As an example of the last-mentioned anthrapyridone dye intermediates, mention may be made of the sulfonyl chloride derivative of N-CH;

As examples of compounds within the aforementioned formula X-Y-Z, mention may be made of the follow- Amino-ethyl-hydroquinone, the preparation of which is disclosed in the copending U.S. application of Milton Green, Serial No. 514,095, filed June 8, 1955;

Amino-phenethyl-hydroquinone, the preparation of which is disclosed in the copending U.S. application of Elkan R. Blout, Milton Green, Howard G. Rogers, Myron S. Simon and Robert B. Woodward, Serial No. 612,051, filed September 25, 1956; and in a continuationin-part thereof, Serial No. 98,287, filed March 27, 1961, now U.S. Patent No. 3,019,107;

Amino-phenethyl-thio-hydroquinone, the preparation of which is disclosed in the copending U.S. application of Milton Green and Howard G. Rogers, Serial No. 663,876, filed June 6, 1957, now U.S. Patent No. 3,009,958;

Amino-phenoxy-hydroquinone, the preparation of which is disclosed in the copending U.S. application of Milton Green and Warren E. Solodar, Serial No. 680,406, filed August 26, 1957;

Amino-propyl-amino-hydroquinone, the preparation of which is disclosed in the copending U.S. application of Milton Green and Myron S. Simon, Serial No. 711,812, filed January 29, 1958, now U.S. Patent No. 3,002,997; and

Amino-hydroquinone, amino-phenyl-hydroquinone, and amino-phenyl-sulfonyl-hydroquinone, etc., which may be prepared by known chemical reactions.

In addition, the aforementioned anthrapyridone dye developers may be prepared by effecting a condensation reaction between an anthrapyridone dye having substituted thereon one or more primary and/or secondary amino groups and a compound of the formula:

wherein Y and Z have the same significance as previously noted and W represents an acid chloride or sulfonyl chloride group.

The enumeration and preparation of compounds within the last-mentioned formula are set forth in the following copending U.S. applications:

Serial No. 471,542, filed November 26, 1954, in the names of Elkan R. Blout, Saul G. Cohen, Milton Green, Howard G. Rogers, Myron S. Simon, and Robert B.

9 r Woodward, and now abandoned, and. in Serial No. 1,442 and 1,443, both filed lanuary 11, 1960, and each a continuation-impart thereof; and

Serial No. 771,718, filed November 4, 1958, in the names of Elkan R. Blout and Richard S. Corley and now abandoned.

It may be desirable to protect the hydroxyl and/r amino groups of the developing function, during the above-mentioned reactions, to avoid undesirable side reactions, that is to employ a protected derivative of Z. The protected derivatives of. Z- set forth in formula X--Y-Z may be prepared by the selective acylation of Z according to the procedure disclosed" in the copending US. application of Milton Green and Helen P. Husek, Serial'No. 612,063, filed September 25, 1956, and which was abandoned in favor of Serial No. 805,673, filed April 13, 1959, now US. Patent No. 3,0l9j,254. The protected derivatives of Z set forth in formula W--Y--Z may be prepared by conventional acylation of Z according to procedures Well known to the art. After reaction and prior to use as a photographic dye developer, the acyloxy groups may be removed by deesterification as, for example, by hydrolysis in the presence. of alkali.

The following examples show by Way of illustration and not by way or limitation the preparation of novel dye developers within the scope of this invention.

Example 1,

en -o I Nr-CHrCHr on NHGHz-CH2- on whose spectral absorption curve in ethanol exhibits absorption maxirna at 514 Inn and 545 mp.

Example 2 24.2 g. (.10 mole) of leucoquinizarin, 60.0 g. (.225 mole) of amino-phenethyl-hydroquinone hydrochloride, 12.4 g. (.2 mole) of boric acid, 21.0 g. (.25 mole) of sodium bicarbonate, and 250 ml. of methyl Cellosolvewere mixed together and refluxed under a blanket of nitrogen for about 20 hours with stirring. 24.6 g. (.1 mole) of, practical grade chloranil was then added and refluxing was continued until oxidation was complete. The mixture was then cooled, filtered, and the filtrate poured into excess dilute hydrochloric acid to yield a precipitate. This precipitate was filtered off, rinsed with cold water and dried to yield 56.1 g. of a cyan dye developer, 1,4-bis-[4'-B-(2",5"-dihydroxyphenyl)-ethyl] anillno-anthraquinone, havinga melting-point of 205 C., exhibiting a spectral absorption curve in ethanol having a. X of 652 mp and 607m e,=.1'7,00,0 andhaving the following, structural formula:

33.2 g. (.05 mole) of the above compound and 600 ml. of benzene were, refluxed through a water trap until dry. The trap was removed and 01.5 ml. of pyridine and the 55 ml. (.77 mole) of acetylchloride were slowly added 'over a 15 minute period and refluxingwas continued while using a, CaCl tube to exclude moisture. After refluxing for an hour, an additional 50 ml. of acetyl chloride was added and refluxing was continued for another 15 hours. The mixture was then cooled, decanted from the sludge and evaporated dry. The residue was redissolved in about 250-350 ml. of benzene, the solution filtered, and the filtrate poured into 3 l. of hexane, the resulting pink precipitate was filtered oil and dried to yield 22.5 g. ofthe acetyl derivative, a pink solid meltingat110-l 15 C., 22.5 g. (.0246 mole) of the acetyl derivative was dissolved in 250 ml. of methyl Cellosolve at room temperature and the mixture was brought to reflux under a blanket of nitrogen. A deaerated solution of 10 g. (.179' mole) of potassium hydroxide in 20 ml. of water was added dropwise to the refluxing solution under nitrogen over a period of 3' to 5 minutes and the reflux was then, continued for an additional 10 to 15 minutes. The solution was then allowed to cool, poured quickly into excess dilute hydrochloric acid to form a precipitate which was filtered off, rinsed and dried. The precipitate was then crystallized from methyl Cellosolve to yield 4.6 g. of a dark purple solid, 3-[4'--(2",5"-dihydroxyphenyl)-ethyl]-phenyl-6-[4'-p (2",5",dihydroxyphenyl)-ethyl]-anilino-anthrapyridone, which melted at 256-258 C., was soluble in pyridine, dimethyl formamide and dilute alkali, and has the following structural formula:

NED-@CHFCHPQ of nitrogen in 50 ml. of methyl Cellosolve. A nitrogendeaerated solution of 5.6 g. (.1 mole) of potassium hydroxide in 20 ml. of methyl Cellosolve and ml. of water was added under nitrogen over a period of 3 minutes. Reflux was then continued for an additional 7 minutes, after which the solution was cooled for minutes and 10 ml. of acetic acid was added. The solution was then poured into 1 1. of dilute acetic acid to precipitate out a magenta solid, which was filtered off and dried to yield .1 g. of crude product. Purification by chromatography yielded 1.55 g. of 3-[fi-(2',5-dihydroxyphenyl)art-methyl]- ethyl-6- [,B- (2,5'-dihydroxyphenyl -u-methyl] -ethylamino- 'anthrapyridone, having the following structural formula:

and a spectral absorption curve in methyl Cellosolve exhibiting absorption maxima at 542 and 510 m e=l2,200.

Example 4 A mixture of 24.0 g. (.10 mole) of quinizarin, 60.0 g. (.226 mole) of amino-phenethyl-hydroquinone hydrochloride, 12.4 g. (.20 mole) of sodium bicarbonate and 21.0 g. of boric acid in 250 ml. of pyridine was refluxed under nitrogen for about 48 hours until no further change in the visible spectrum was observed. The mixture was then cooled under an atmosphere of nitrogen and filtered. The filtrate was poured into a large volume of an excess of cold dilute hydrochloric acid with vigorous stirring. The precipitate was filtered oh and dried to yield 43 g. or" 4 [4 p-(2",5"-dihydroxyphenyl)ethyl]-anilino-1-hydroxy-anthraquinone, having the following structural formula:

A mixture of 20.0 g. (.0443 mole) of the above compound, 14.84 g. (.060 mole) of fi-(2,5-dihydroxyphenyl)- m-methyl-ethylamine hydrobromide, 5.13 g. (.061 mole) of sodium bicarbonate, and 200 ml. of methyl Cellosolve was refluxed under a blanket of nitrogen, thereby evolving carbon dioxide gas. When the evolution of gas ceased, 10 ml. of acetic acid was added and refluxing was continued for 24-48 hours until no further change in the visible spectrum was observed. The mixture was then cooled under nitrogen, filtered, and the filtrate poured into a large volume of cold dilute hydrochloric acid with vigorous stirring. The resulting precipitate was filtered 12 off and vacuum dried to yield a crude product, 1-[fl-(2',5'- dihydroxyphenyl) a-methyl]-ethylarnino-4-[4-;3-(2",S"- dihydroxyphenyl)ethyl]-anilino-anthraquinone of the foliowing structural formula:

OH OH;

I O NH 011- C H2- I I OH The last-mentioned product was purified by precipitation into hexane from ethyl acetate solution followed by repeated extractions in acetone and evaporations until dry, until 8 g. of purified product was recovered. 6.5 g. of the purified product (.0108 mole), 23 ml. (.324 mole) of acetyl chloride and 270 ml. of dry benzene were refluxed together on a steam bath for about 24 hours until the )t of the solution was about 500 me. This solution was then cooled and filtered and the residue was rinsed with benzene. The rinsings were also filtered and the filtrates were then combined and precipitated into about 3 l. of hexane. The precipitate was filtered oil and vacuum dried to yield 6.7 g. of acetylated anthraquinone product. 4 g. of this product was refluxed in 40 ml. of methyl Cellosolve under a blanket of nitrogen. A deaerated solution of 3.92 g. (.07 mole) of potassium hydroxide in 4 ml. of water was then added under nitrogen during a one minute period. The reflux was continued for another 4 minutes, then the mixture was cooled, acidified with acetic acid and precipitated into cold dilute hydrochloric acid with vigorous stirring. The precipitate was then filtered and dried to yield 3.2 g. of crude product. Purification by chromatography gave two separate fractions: (1) 3 [B-(2',5-dihydroxyphenyl)-ot-methyl]-ethyl-6-[4- B (2",5" dihydroxyphenyl) ethyl]-anilino-anthrapyridone, having the following structural formula:

. 13 V 6.- [3- (2,,5 -dihydroxyphenyllmethyll-ethylaminm anthrapyridone, having the, following structural formula:

only, proportions being by weight unless otherwise indicated, are:

Example A photosensitive element is prepared by coating a gelatin coated, film base with a solution comprising:

Acetone 50 Tetrahydrofuran 50 Cellulose acetate hydrogen phthalate 4 1 acetyl 3-p-(2f,5'-dihydroxyphenyl)ethyl-Sp-(2',

5'-dihydroxypheuyl)-ethylamino-anthrapyridone 3.8

' After this coating has dried, a silver iodobromide emulsion is applied. The photosensitive element is exposed and an aqueous liquid processing composition comprising:

. Percent Sodium carboxymethyl cellulose 4.5 l-phenyl-3-pyrazolidone 0.2 Sodium hydroxide u 2.0 Potassium bromide 0.2

is spread between the exposed photosensitive element and an image-receiving element as said elements are brought into superposed relationship. The image-receiving element comprises a cellulose acetate-coated baryta paper which has. been coated with a 6% aqueous polyvinyl alcoholsolutionl After an imbibition period of approximately one minute, the image-receiving element is separated and is found to contain a reddishpinlc, positive image of the photographed subject matter.

Example 6 Percent Sodium carboxymethyl cellulose 4.5 Potassium bromide 0.2 Sodium hydroxide V 1.5 l-phenyl-S-pyrazolidone 0.2

gives a magenta, positive image on a superposed imagereceiving element prepared as described in Example 2.

14 Example 7 A photosensitive element was prepared by coating a gelatin subcoated cellulose; acetate film base with a solution comprising 0.25 g. of 3-[fi-(2,5-dihydroxyphenyl)-amethyl} ethyl 6 [4f ,8 (2",5" dihydroxyphenyD- ethyll-anilino-anthrapyridone, dissolved in 10 cc. of a solution of 4% cellulose acetate hydrogen phthalate in a 50:50mixture, by volume, of methanol and tetrahydrofuran. After this coating dried, a green-sensitive silver iodobromide. emulsion was applied and allowed to dry. This. photosensitiveelement was exposed and brought into superposed relationship with an image-receiving element as an aqueous composition comprising:

Water cc NaOH V g-.. 5.17 Hydroxy cellulose (high viscosity) [commercially available from Hercules Power Co., under the trade name Natrosol 2 5O] g 4.03 Sodium thiosulfate u g 1.15 Benzotriazole g 2.3 N-benzyl-a-picolinium bromide r g 2.3

was spread between said elements. The image-receiving element comprised a 2:1 mixture by weight of polyvinyl alcohol and pol -4-vinylpyridine on a baryta paper support. After an imbibition period of approximately one minute, the image-receiving element was separated and contained a magenta positive image.

Example 8 Water cc 100 NaOH g 3.0

Hydroxyethyl cellulose (high viscosity) [commercially available from Hercules Powder 00., under the trade name Natrosol 250] g 3.5 Sodium thiosulfate g 1.2 Benzotriazole -g 1.5 N-benzyl-e-picolinium bromide g 2.3

was spread between said elements. The. image-receiving element comprised a 2:1 mixture by weight of polyvinyl alcohol and poly-4-vinylpyridine on a baryta paper support. After an imbibition period of approximately one minute, the image-receiving elementwas separated and contained a magentapositive image.

It will be appreciated that the dye developers may, for example, be dispersed in a layer of gelatin in lieu of the procedures described in the aforementioned photographic examples. This dispersion may be made by procedures known in, the art. For example, the dispersion may be made by dissolving the dye developer in a suitable organic solvent or mixtureof solvents and agitating this solution in a Waring Blender with an aqueous gelatin solution and. a suitable dispersing agent. The resulting dispersion may be. diluted, if desired, and coated onto a gelatin subcoated. film base in the manner heretofore described.

The dye developers of this invention are also useful in integral multilayer photosensitive. elements for use in multicolor diffusion transfer processes. As an example of such photosensitive elements, mention may be made of the photosensitive elements disclosed and claimed in the copending- US. application of Edwin H. Land and Howard G. Rogers, Serial No. 565,135, filed February 13,

aoveeos 1956, wherein at least two selectively sensitized photoensitive strata are superposed on a single support and are processed, simultaneously and without separation, with a single common image-receiving element. A suitable arran ement of this type comprises a support carrying a red-sensitive silver halide emulsion stratum, a green-sensitive silver halide emulsion stratum and a blue-sensitive silver halide emulsion stratum, said emulsions having as sociated therewith, respectively, a cyan dye developer, at magenta dye developer and a yellow dye developer. In one of the preferred embodiments of photosensitive elements of this type, the dye developers are disposed in separate alkali-permeable layers behind the photosensitive silver halide emulsion stratum with which they are associated.

The photosensitive elements within the scope of this invention may be used in roll film units which contain a plurality of photosensitive frames. The photosensitive elements or this invention are especially useful in composite roll film intended for use in a Polaroid Land Camera, sold by Polaroid Corporation, Cambridge 39, Massachusetts, or a similar camera structure such, for example, as the camera forming the subject matter of U.S. Patent No. 2,435,717, issued to Edwin H. Land on February 10, 1948. in general, such composite roll films comprise a photosensitive roll, a roll of image-receiving material and a plurality of pods containing an aqueous alkaline processing solution. The rolls and pods are so associated with each other that, upon processing, the photosensitive element my be superposed on the image-receiving element and the pods may be ruptured to spread the aqueous alkaline processing solution between the superposed elements. The nature and construction of the pods used in such units are well known to the art. See, for example, US. Patents Nos. 2,543,181 and 2,634,886, issued to Edwin E. Land.

it will be noted that the liquid processing composition may contain one or more auxiliary or accelerating silver halide developing agents, such as p-methylaminophenol (Metol); 2,4-diaminophenol (Amidol); benzylarninophenol', hydroquinone; a substituted hydroquinone such as toluhydroquinone, phenylhydroquinone, or 4'-methylphenylhydroquinone; or a 3-pyrazolidone such as l-phenyl-3-pyrazolidone. These silver halide developing agents are substantially colorless, at least in their unoxidized form. It is possible that some of the dye developer oxidized in exposed areas may be oxidized by an energy transfer reaction with oxidized auxiliary developing agent.

In addition, development may be eifected in the presence of an onium compound, particularly a quaternary ammonium compound, in accordance with the processes disclosed and claimed in the copending application of Milton Green and Howard G. Rogers, Serial No. 50,851, filed August 22, 1960.

The dye developers of this invention may be used also in conventional photographic processes, such as tray or tank development of conventional photosensitive films, plates or papers to obtain black-and-white, monochromatic or toned prints or negatives. By way of example, a developer composition suitable for such use may comprise an aqueous solution of approximately 1-2% of the dye developer, 1% sodium hydroxide, 2% sodium sulfite and 0.05% potassium bromide. After development is completed, any unreacted dye developer is Washed out of the photosensitive element, preferably with an alkaline washing medium or other medium in which the unreacted dye developer is soluble. The expression toned is used to designate photographic images wherein the silver is retained with the precipitated dye whereas monochromatic is intended to designate dye images free of silver.

It should be noted that the dye developers of this medium are seli-sufiicient to provide the desired color image and do not depend upon coupling reactions to produce the desired color. They thus provide a complete departure from conventional photographic color processes in which id the color is produced bya coupling reaction between a color former or coupler and the oxidized developing agent, as well as so-called auto-coupling processes in which color is obtained by a reaction or the oxidized developing agent with unoxidized developing agent.

It will be apparent that, by appropriate selection of the image-receiving element from among suitable known opaque and transparent materials, it is possible to obtain either a colored positive reflection print or a colored positive transparency. Likewise, the inventive concepts herein set forth are adaptable for multicolor work by the use of special photographic materials, for example, film materials of the type containing two or more photosensitized elements associated with an appropriate number of imagerecciving elements and adapted to be treated with one or more liquid processing compositions, appropriate dye developers suitable to impart the desired subtractive colors being incorporated in the photosensitized elements or in the liquid processing compositions. Examples of such photographic materials are disclosed in U.S. Patent No. 2,647,049 to Edwin H. Land.

As examples of useful image-receiving materials, mention may be made of nylon, e.g., N-methoxymethyl-polyhexamethyiene adipamide, polyvinyl alcohol, and gelatin, particularly polyvinyl alcohol or gelatin containing a dye mordant such as polyl-vinylpyridine. The image-receiving element also may contain a development restrainer, e.g., l-phenyl-5-mercaptotetrazole, as disclosed in the copending application of Howard G. Rogers and Harriet W. Lutes, Serial No. 50,849, filed August 22, 1960.

The dye developers here-in set forth are also useful in the formation of colored images in accordance with the photographic products and processes described and claimed in U.S. Patent No. 2,968,554, issued to Edwin H. Land on January 17, 1961.

The novel compounds herein disclosed are also suitable for use as dyes for textile fibres, such as nylon.

In the preceding portions of the specification, the expression color has been frequently used. This expression is intended to include the use of a plurality of colors to obtain black.

This application is in. part a continuation of our copending application, Serial No. 799,425, filed March 16, 1959, and now abandoned, which in turn is in part a continuation of application Serial No. 522,843, filed July 18, 1955, and now abandoned.

Our copending U.S. application, Serial No. 150,657, filed November 11, 1961, claims the photographic utilization of the novel compounds of the present invention.

Since certain changes may be made in the above products, compositions and processes without departing from the scope of the invention herein involved, it is intended that all matter contained in the above description shall be interpreted as illustrative and not in a limiting sense.

What is claimed is:

1. A dye developer of the formula:

wherein R is selected from the group consisting of hydrogen and acetyl; R is selected from the group consisting of benzene and naphthalene snuclei substituted by two groups the group consisting of hydrogen and --Y--Z; Y is a divalent organic linking group selected from the group con sisting of lower alkylene, phenylene, and

lower alkylene Z is an aryl nucleus selected from the group consisting of benzene and naphthaleen nuclei substituted by two groups selected from the group consisting of hydroxyl and amino groups, one of said groups being substituted in one of the ortho and para positions with respect to the other of said groups so as to be capable of developing an exposed silver halide emulsion and at least one of said R and R is -Y--Z.

2. "1-acety1-3fi-(2',5' dihydroxyphenyl) ethyl-6 942, S'-dihydroxyphenyl)-ethylarnino-anthrapyridone.

3. 3-[,B-(Z,5 dihydroxyphenyl)-u-methyl]-ethyl-6-]fl- (2',5-dihydroxyphenyl)-a-methyl] ethylamino anthrapyridone.

4. 3-[,8-(2',5'-dihydroxyphenyl) a methyH-ethyl-G- [4'-;3-(2",5-dihydroxyphenyl) ethyl] aniline-anthrapyridone.

5. 3-[4' B (2,5"-dihydroxyphenyl)-ethyl]-phenyl- 6-[B (2,S'-dihydroxyphenyl)-a-methy1] ethylamino-anthrapyridone.

6. 3-[4'-p-(2",5" dihydroxyphenyl) ethyl]-phenyl- 6-[4'-;9-(2-5"-dihydroxyphenyl)-ethyl] anilino-anthrapyridone.

7. The process of preparing 3-[fl-(2',S'-dihydroxyphenyl)-a-methyl]-ethyl 6 [l8 (2',5 dihydroxyphenyl)-umethyl]-ethylamino-anthrapyridone which comprises acetylating 1,4-bis-[B-(2,5'-dihydroxyphenyl)a-methyH-ethylamino-anthraquinone by refluxing with acetyl chloride, and internally condensing said last-named compound to effect cyclization thereof, thereby forming said pyrimidone.

8. The process of forming a compound selected from the group consisting of 3-(fl-(2,5-dihydroxyphenyl)-amethyl] ethy1-6- [4-B-(2",5" dihydroxyphenyl)-ethyl]- anilin-o-anthrapyridone and 3-[4 B (2",5"-dihydroxyphenyl)-ethyl]-phenyl 6 [B-(2,5'-dihydroxyphenyl)-amethyl]-ethylamino-anthrapyridone which comprises refluxing quinizarin with amino-phenethyl-hydroquinone hydrochloride in an inert atmosphere; refluxing the resulting product with fl-(2,5-dihydroxyphenyl) a methyl-ethylamine hydrobromide in an inert atmosphere to form a 1,4- bis-substituted anthraquinone dye developer, acetylating said dye developer by refluxing with acetyl chloride; and condensing the acetylated reaction product to efiect cyclization thereof, thereby forming an isomeric mixture comprising 3-[ 8-(2',5'-dihydroxyphenyl) a methylJ-ethyl-G [fl-(2',5'-dihydroxyphenyl) a methyl] -ethy-larnino anthrapyridone and 3-[,B-(2',5-dihydroxyphenyl)-u-methyl]-ethyl 6 [4' 8-(2,5-dihydroxyphenyl)-ethyl]-anilino-anthrapyridone.

9. The process which comprises acetylating 1,4-bis-[4'- fi-(2",5" dihydroxyphenyl) ethyl]-anilinoanthraquinone to form 1,4-bis-(2',5-diacetoxy)-phenethyl-acetanilido-anthraquinone and condensing said last-named compound, thereby efiecting cyclization thereof, to form 3- [4-/3-(2",5"-dihydroxyphenyl)-ethyl] phenyl 6[4-B- (2",5 "-dihydroxyphenyl) -et-hyl] -anilino-anthrapyridone.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No 3,076,808 February 5, 1963 Elkan R Blout et al.

It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 6, line 41, for "absorp" read absorb column 8, line 41, after "September 25, 1956" insert now U. So Patent No. 3,019,107 lines 42 and 43, strike out -n-ow U0 So Patent Non 3,019,107 column 10, line 66, for "542" read 532 column 14, line 17, for "Hydroxy" read Hydroxyetbyl column 16, line 74, for "benzene and naphthalene snuclei subsgituted by two groups" read hydrogen, lower alkyl and -Y-'Z; R is selected from column 17, line 10, for "naphthaleen" read naphthalene column 18, line 4, for "ii-(E read 3[B Signed and sealed this 26th day of November 19630 (SEAL) Anew I EDWIN La REYNOLDS ERNEST W. SWIDER Attesting Officer A ti g Commissioner of Patents 

1. A DYE DEVELOPER OF THE FORMULA: 